Pyrazolo-(thiono)-phosphoric(phosphonic)acid esters

ABSTRACT

1. A PYRAZOLO-(THIONO) - PHOSPHORIC(PHOSPHONIC) ACID ESTER OF THE FORMULA   1-(CH3-),3-(R-O-P(=Y)(-R1)-O-),4-(NC-),5-(R2-S-)-PYRAZOLE IN WHICH R IS ALKYL OF 1-6 CARBON ATOMS, R1 IS ALKYL OR ALKOXY OF 1-6 CARBON ATOMS, R2 IS ALKYL OF 2-4 CARBON ATOMS, AND Y IS OXYGEN OR SULFUR.

United States Patent US. 01. 260-310 R 9 Claims ABSTRACT OF THEDISCLOSURE Pyrazolo-(thiono)-phosphoric(phosphonic) acid esters of thegeneral formula in which R is alkyl with 1-6 carbon atoms,

R is alkyl or alkoxy with 1-6 carbon atoms, R;', is alkyl with 2-4carbon atoms, and

Y is oxyen or sulfur,

which possess insecticidal, acaricidal, rodenticidal, fungicidal andnematocidal properties.

The present invention relates to and has for its objects the provisionof particular new pyrazolo-(thiono)-phos phoric(phosphonic) acid esters,i.e. 0,0-dialkyl-O-[1- methyl-4 Cyano-S-ethyl-(or propylorbutyl-)mercaptopyrazol(3)yl] (thiono)phosphoric acid esters and thecorresponding alkanephosphonic acid esters, which possess insecticidal,acaricidal, rodenticidal, fungicidal and nematocidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. insects, acarids, rodents, fungi and nematodes,especially insects and acarids, with other and further objects becomingapparent from a study ofthe within specification and accompanyingexamples.

From US. Patent Specification 2,754,244 it is known thatmethylpyrazolo-(thiono)-phosphoric acid esters, such an 0,0 dimethyl-(Compound A) or 0,0-diethyl-O-[5- methylpyrazol(3)yl]-thionophosphoricacid ester (Compound B), possess aninsecticidal and acaricidal activity.

The present invention provides pyrazolo-(thiono)-phosphoric(phosphonic)acid esters of the formula in which R is alkyl with 1-6 carbon atoms,

R, is alkyl or alkoxy with 1-6 carbon atoms, R is alkyl with 2-4 carbonatoms, and

Y is oxygen or sulfur.

3,839,355 Patented Oct. 1, 1974 ICC It has surprisingly been found thatthese compounds exhibit strong insecticidal and acaricidal propertiesand often stronglrodenticidal, fungicidal and nematocidal properties, aswel The invention also provides a process for the production of apyrazolo-(thiono)-phosphoric(phosphonic)acid ester of the formula (I) inwhich a (thiono)phosphoric (phosphonic) acid ester halide of the formulaROY i -Hal is reacted with a 1methyl-3-hydroxy-4-cyano-5-alkylmercaptopyrazole of the formula JJH;(III) in the form of a salt or in the presence of an acid-binding agent,

R, R R and Y in the aforesaid formulae possessing the meanings statedabove, while Hal stands for halogen, preferably chlorine.

Surprisingly, the pyrazolo-(thiono)-phosphoric(phosphonic) acid estersaccording to the invention are distinguished by a considerably betterinsecticidal, in particular soil-insecticidal, and acaricidal, activitythan the known methylpyrazolo-(thiono)-phosphoric acid esters ofanalogous constitution and the same direction of activity. The compoundsaccording to the invention therefore represent a genuine enrichment ofthe art.

If, for example, 0,0-diethylthionophosphoric acid diester chloride and lmethyl-3-hydroxy-4-cyano-5-ethylmercaptopyrazole are used as startingmaterials, the reaction course can be represented by the followingformula scheme:

In the foregoing formulae, R and R preferably are straight-chain orbranched lower alkyl radicals with 1 to 4 carbon atoms, such as methyl,ethyl, nor iso-propyl, or n-, iso-, sec.- or tert.butyl. Alternatively,R may also preferably be a lower alkoxy group with 1 to 4 carbon atoms.R is preferably ethyl, propyl or iso-propyl.

As examples of the (thiono)-phosphoric(phosphonic) acid ester halides(II) to be used according to the process there are mentioned inparticular:

0,0-dimethy1-, 0,0-diethyl-, 0,0-dipropy1-, 0,0-di-iso-propy1-,O-methy1-O-ethyl-, O-methyl-O-iso-propyl-,

. O-ethyl-O-isopropyl-phosphoric acid ester chloride or the appropriatethiono analogues;

further,

O-methyl-methane-,

O-ethyl-propane-,

O-iso-propyl-ethane-,

O-butyl-methane-phosphom'c acid ester chloride and the appropriatethiono compounds.

The (thiono) phosphoric (phosphonic) acid ester halides of theconstitution (II) required as starting materials are known from theliterature and, like the pyrazole derivative of the constitution (III)whose synthesis is described in Example 7 hereinbelow, are readilyaccessible, even on an industrial scale.

The preparative process is preferably carried out with the use ofsuitable solvents or diluents. As such, practically all inert organicsolvents are suitable. These include, in particular, aliphatic andaromatic optionally chlorinated hydrocarbons, such as benzene, toluene,xylene, benzine, methylene chloride, chloroform, carbontetrachloride,chlorobenzene; ethers, such as diethyl and dibutyl ether, dioxane;ketones, for example acetone, methyl ethyl, methylisopropyl andmethylisobutyl ketone; and nitriles, such as acetoand propionitrile.

As acid acceptors, all customary acid-binding agents can be used.Particularly good results have been obtained with alkali metalcarbonates and alcoholates, such as sodium and potassium carbonate,methylate or ethylate; further, aliphatic, aromatic or heterocyclicamines, for example triethylamine, dimethylamine, dimethylaniline,dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly Wide range. Ingeneral, the reaction is carried out at about 40 to 120, preferably atabout 75 to 85 C.

The reaction is, in general, carried out at normal pressure.

For carrying out of the process, the starting materials are in mostcases used in equimolar proportions. An excess of one or other of thereaction components brings no substantial advantages. The reaction ispreferably carried out in the presence of one of the above-mentionedsolvents, as well as in the presence of an acid acceptor, at thetemperatures stated. After several hours stirringoptionally withheating-the reaction mixture is poured into water, taken up with ahydrocarbon, preferably benzene, and worked up in accordance withcustomary processes.

The products according to the invention are obtained in most cases inthe form of colorless to slightly yellow colored, viscous,water-insoluble oils which cannot be distilled without decomposition butcan, by so-called slight distillation, that is, by longer heating tomoderately elevated temperatures, be freed from the last volatilecomponents and in this way be pun'fied. For their characterization therefractive index is especially useful.

As already mentioned above, the newpyrazolo-(thiono)phosphoric(phosphonic) acid esters are distinguished byan outstanding insecticidal and acaricidal effectiveness against croppests, hygiene pests and pests of stored products. They possess a goodactivity against both sucking and eating insects and mites (Acarina). Atthe same time, they exhibit a low phytotoxicity. Often they exhibitsubstantial rodenticidal, fungicidal and nematocidal activity. Theproducts according to the invention are therefore useful as pesticides,above all in crop protection and the protection of stored products, aswell as in the hygiene field.

To the sucking insects contemplated herein there be- (Aspidiotushederae) and the soft scale (Lecamiim hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex lectularius), the assassin bug (Rhodnius prolz'xus) and Chagasbug (T riatoma infestans) and,

further, cicadas, such as Euscelis bilobatus and Nephotet- I tixbipunctatus; and the like. i v I In the case of the biting insectscontemplated herein, above all there should be mentioned butterflycaterpillars (Lepz'doptera) such as the diamond-back moth (Plutellamaculipennis), the gypsy moth (Lymantria dispar), the brown-tail moth(Euproctz's chrysorrhoea) and tent caterpillar (Malacosoma neustrz'a);further, the cabbage moth (Manzestra brassicae) and the cutworm (Agrotissegetum), the large white butterfly (Pieris brassicae), the small Iwinter moth (Cheimat bia brumata), the 'greenoaktortrix moth (Tortrz'xviridana), the fall armyworm (Laphygma frugiperda) and cotton worm(Prodenia litura), the ermine moth (Hyponomeuta padella), theMediterranean flour moth (Ephestia kt'ihniella) and greater wax beetle(Dermestes frischi), the khapra beetle (Tr0g0d-- erma granarium), theflour beetle (Tribolium casteneum),

the northern corn billbug (Calandra or Sitophilu's zeamais), thedrugstore beetle (Stegobium paniceum), the

yellow mealworm (Tenebrio molitor) and the sawtoothed grain beetle(Oryzaephilus surinamensis), and also species living in the soil, forexample wireworms (Agriores spec.) and larvae of the cockchafer(Melolontha melolontha); cockroaches, such as the German cockroach(Blattella germanz'ca), American cockroach (Periplaneta americana),Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach(Blatta orientalis), the giant cockroach (Blaberus gigan-.

tens) and the black giant cockroach '(Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the housecricket (Acheta domesticus); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fannia canicularz's), the black blow fly (Phormia regina) andblue-bottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegyp'z't), the northern house mosquito(Culex pipiens) and the malaria mosquito {Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein'there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius =Tetranychus althaeae 0r Tetranychusurticae) and the European red mite (Paratetranychus pil0sus=Panonychusulmi), gall mites, for example the black currant gall mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornitlzodorus moubata); and the like.

When applied against hygiene pests and pests of stored products,particularly flies and mosquitoes, the novel-= products are alsodistinguished by an outstandingresidual' activity on wood and clay, aswell as a good stability to liquid diluent carriers and/or dispersiblesolid carriers optionally with the use of carrier vehicle assistants,e.g. conventional pesticide surface-active agents, including emulsifyingagents and/ or dispersing agents, whereby,'for example, in the casewhere water is used as diluent organic solvents may be added asauxiliary solvents. The following may be chiefly considered for use asconventional carrier vehicles for this purpose: aerosol propellantswhich are gaseous at normal temperatures and pressure, such as Freon;inert dispersible liquid diluent carriers, including inert organicsolvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/or anionic emulsifying agents (e.g. polyethyleen oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other insecticides,acaricides rodenticides, fungicides and nematocides, or bactericides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in 'which the active compoundis present in an amount sub- 'stantially between about 01-95% by weight,and preferably 0.5-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.000l-%, preferably0.01l%, by weight of the mixture. Thus, the present inventioncontemplates over-all compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersible inertfinely divided carrier solid, and/or (2) a dispersible carrier liquidsuch as an inert organic solvent and/or water preferably including asurface-active effec- 6 tive amount of a carrier vehicle assistant, e.g.a surfaceactive agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.000135%, andpreferably 0.01-%, by.weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50- microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g./hectare, preferably 40to 600 g./hectare, are suflicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids, rodents,fungi and nematodes and n ore particularly methods of combating at leastone of insects and acarids, which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, (e) such rodents,(d) such fungi, (e) such nematodes and (f) the corresponding habitatthereof, i.e. the locus to be protected, a correspondingly combative ortoxic amount, i.e. an insecticidally, acaricidally, rodenticidally,fungicidally, or nematocidally effective amount of the particular activecompound of the invention alone or together with a carrier vehicle asnoted above. The instant formulations or compositions are applied in theusual manner, for instance by spraying, atomizing, vaporizing,scattering, dusting, watering, squirting, sprinkling, pouring,fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1part by weight alkylaryl polyglycol ether To produce a suitablepreparation of active compound, 1 part by weight of the active compoundis mixed with the stated amount of solvent containing the stated amountof emulsifier and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamond-back moth (Plutella maculipennz's).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from Table l.

. A L LU I. 5

Concentrae; TB; tion of ac- Degree of tive comdestruction -poun'dininpercent Active compound- (c onstitution) J percent aiteriidays (B).--"r-CHS 0.1 100 I 0.01

. NH I I (C2H50)z]? O N (Known).

(A)-.- S -CH3 0.1

n NH (CHgOhP-O N (Known) (2)---- NC- S 02115 0. 1 100 u 0.01 100 N-CHaCH O) PO z 2 N (1) No S CzH 0. 1 100 H 0.01 100 NCH: O H O) PO 2 a z N(3)---- NC S C2H5 0. 1 100 H 0.01 100 o2rr.-P-o- N-CH@ (4)...- NC- SC2H5O. 1 100 I 0.01 100 NOHa (C2H5O)zP--O \N/ EXAMPLE 2 Myzus test (contactaction) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weightal=kylarylpolyg1ycol ether To produce a suitable preparation of activecompound, 1 part by Weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier andthe concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the aphids are killedwhereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theelevation times and the results can be seen from the following Table 2:

TABLE 2.MYZ US TEST pound; in. in percent #OtjYqOinRofipti(constitution) 3 percent, after; days EXAMPLE 3 Tetranychus testSolvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylaryl polyglycol ethe To produce a suitable preparation of activecompound, 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated'amount of emulsifier andthe concentrate so obtained is diluted with water to the desiredconcentration. v

Bean plants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(T etranychus urlicae) in all stages of development.

After the specified periods of time, the efi'ectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage;means that all the spider mites are killed whereas 0% means that none ofthe spider mites are killed. v I i The active compounds, theconcentrations of the active compounds, the evaluation times and theresults can be seen from Table 3:

TAB LE 3.TET RANYCH US TEST Concentra Degree of tion of activedestruction compound in percent Active compound (constitution) inpercent after 2 days (B)--- -OH3 0. 1 0

ll NH (C2H5O)2P-O\\N/ (Known) (A)--- S OH; 0.1 0

ll H (CHa0)2PO N (Known) (2).--- NC- -S CgH 0. 1 100 H 0. 01 100 omo)21--o.

(1)---- NC S C2H5' 0. 1 w 100 H 0. 01 ".100 o2n50)z1 -o- 3).... NC- sCzHs o. 1 'j 100 v i 0. 01 100 N-OH 02H Y-PO :N/ CzH5O r (4).--- NC S02H. 0.1 100 fl) =0. 01 70 (o2H5o).P-o-

9 EXAMPLE 4 Critical concentration test/ soil insects Test insect:cabbage root fly maggots (Phorbia brassicae) Solvent: 3 parts by weightacetone Emulsifier: 1 part by weight alkylarylpolyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofactive compound is mixed with the stated amount of solvent,.the statedamount of emulsifier is added and the concentrate is diluted with waterto the desired concentration. The preparation of active compound isintimately mixedwith soil. The concentration of the active compound inthe preparation is of practically no importance; only the amount ofactive compound per unit volume of soil, which is given in ppm. (forexample mg;/l.), is' decisive. The soil is filled into pots and the potsare left to stand at room temperature. After 24 hours, the test animal'sare' put into the treated soiland, after a further 48 hours, the degreeof effectiveness of the active compound is determined as a percentage bycounting the dead and living test insects. The degree of destruction is100% when all the test insects have been killed; it is when exactly asmany test insects are still alive as in the case of the control.

The active compounds,-the amounts applied and the results can be seenfrom the following Table 4:

TABLE 4.-SOIL INSECTICIDES [Phorbic brassicae-maggots] Degree ofdestruction in percent with a concentration of active compoun? in p.p.m.o

Active compound (constitution) 20 10 The following further examples areset forth to illustrate, without limitation, the process for producingthe active compounds according to the present invention.

EXAMPLE 5 8 NC- SC2Ht N-CH: CHM? N 2) To 55 g. (0.3 mole) of1-methyl-3-hydroxy-4-cyano-5- ethylmercapto-pyrazole and 45 g. ofpotassium carbonate in 300 ml. of acetonitrile there are added 48 g.(0.3 mole) of 0,0-dimethyl thionophosphoric acid ester chloride, thetemperature of the mixture being kept at 35 to 40 C. The reactionmixture is subsequently stirred for 3 hours, poured into water, taken upin benzene, the benzene phase is washed until neutral, dried, and, afterthe solvent has been drawn off, the residue is slightly distilled. Thereremain behind 67 g. (73% of theory) of the desired 0,0-dimethyl O[l-methyl 4 cyano 5 -ethylmercapto-pyrazol- (3)yl]-thionophosphoric acidester.

For C H N O PS (molecular weight 307). Calculated: N, 13.7%; S, 20.85%;P, 10.1%. Found: N, 13.9%; S, 20.30%; P, 9.7%.

10 EXAMPLE 6 By a procedure analogous to Example 5, the followingcompounds are prepared:

Yield, Refractive percent Formula index of theory (1).-.- s N C- S 02H;n, =1.5239 87 l N-CHa (CzHsOhP-O \N/ (3)...- 8 NC- s 02H; n,=1.5352 67 lN-CH: C2Hr/-I O \N/ 4 NC- s 02H, n,, =1.5042 s5 N-CH: (C2H5O)ZPO \N/(5)-... 0 NC- s 0 11 1 m =L5194 so H l N-CHa (G2H,o)P-o \N/ (s) S NC- s031111 n,, ==1.5376 79 N cm (CH3O)2PO \N/ (7).... S NC- s can n,#=1.5321 s0 N-om OHaP-O- \N/ iC3H O The l-methyl 3 hydroxy 4cyano-S-ethylmercaptopyrazole required as starting material can beobtained for example as follows:

EXAMPLE 7 g. (0.5 mole) of the compound of the following formula onto-o0soim o=o NC/ SCaHs (V) (prepared according to Chemische Berichte, Vol.95, (1962) 2861 and 2870 by reacting methyl cyanoacetate with carbondisulfide in the presence of an alkali, followed by reaction with twomoles of ethyl halide) are heated together with 23 g. of methylhydrazinein 500 ml. of absolute ethanol for one hour at 70 to 75 C. Ethyl sulfideis distilled off and the reaction solution is cooled. The mixture isthen diluted with 500 ml. of water and the reaction product is allowedto crystallize out. The crystals are filtered off with suction, washedwith ether and dried on clay. There remain behind 50 g. (55% of theory)of the desired substance of melting point 192 C.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. A pyrazolo-(thiono) phosphoric(phosphonic) acid ester of the formulain which R is alkyl of 1-6 carbon atoms, R; is alkyl or alkoxy of 1-6carbon atoms, R is alkyl of 2-4 carbon atoms, and Y is oxygen or sulfur.

'1 1 2. A compound according to claim 1 in which R and R each is of 1-4carbon atoms and R is of 2 or 3 carbon atoms.

3. The compound according to claim 1 wherein such compound is0,0-dimethyl O [1-methy1-4-cyano-5- ethylmercaptopyrazol(3)yl]-thionophosphoric acid ester of the formula NC SCzHs i i I N-CHa CHO) P-O 8 2 \N/ 4. The compound according to claim 1 wherein suchcompound is 0,0-diethyl-O-[1-methyl 4 cyano-5-ethy1-mercaptopyrazol(3)yl]-thionophosphoric acid ester of the formula NC SCzn I czmoni-o 5. The compound according to claim 1 wherein such compoundis O-ethyl-O-[l-methyl 4 cyano 5 ethylmercaptopyrazol(3)yl]-ethanethionophosphonic acid ester of the formula 6. The compoundaccording to claim 1 wherein such compound is 0,0-diethyl-O-[1-methyl 4cyano-S-ethylmercaptopyrazol(3)ylJ-phosphoric acid ester of the formulaNC s 01H Ii I N CH (C2H50)2PO 3 (4) 7. The compound according to claim 1wherein such compound is 0,0-diethyl-O-[1-methyl 4cyano-S-isopropylmercapto-pyrazol(3)y1]-phosphoric acid ester of theformula 9. The compound according to claim 1 wherein such compound isO-isopropyl-O-[Lmethyl 4 cyano 5 is0- propylmercapto pyrazol(3)y1]methan'ethionophosphom' ic acid ester of the formula i 'No $6 1111 CH;\fi

o N-om N iCaHvO r (7).

References Cited I I I I UNITED STATES PATENTS 1,

3,728,297 4/1973 Hofimann et a1. 260-310 R 2,754,244 7/1956 Gysin et a1260-310 R 2,998,426 8/1961 ''Dickinson et al. 26031O R 3 3,111,52511/1963 Meltzer et a1 260--310 R 3,216,894 11/1965 Lorenz et a1.260----310 R FOREIGN PATENTS I I 35 1,942,561 2/1971 Germany 260310 RNATALIE TROUSOF, Primary Examiner I U.S. Cl. X.R.

' UNITED S'lA'l'liS PATENT OFFICE (5/69) r r w w "1 r CERUFICAFL ObCORRLCFION Perm No. 3,839,355 Dated October 1, 197a Inventor) HELLMUTHOFFMANN ET AL It is certified that error appearsin the aboye-idcntifiedpatent and that said Letters Patent are hereby corrected as shown below:

Col. A, line 30, change "beam" to. been Col. 4, line 43 correct spellingof "maueirae Col. 4 line 59, correct spelling of aegvpti".

Col. 5, line 45, correct spelling of "polyethylene".

Col. 7, Table 1, Compound (A) under nee ding "Degree destruction percentafter 3 days, insert O Col. 7, Teble 1, Compound (1) in the structuralformula,

change "N-CH to N-CH Col. 7, line 54, cancel "elevation" and substituteevaluation Col. 8, Table 2, in the heading of the last column in theTable,

cancel "3 days" and substitute 1 day Col. 9, Table 4, before secondstructural formula, insert (35 Signed and Scaled this twenty-second DayOf July 1975 [SEAL] A ties t:

C. MARSHALL DANN Commissioner of Patents and Trademarks RUTH C. MASONAlresn'ng Officer

1. A PYRAZOLO-(THIONO) - PHOSPHORIC(PHOSPHONIC) ACID ESTER OF THEFORMULA